CN114716598A - Preparation method of butadiene-isoprene copolymer, butadiene-isoprene copolymer and tread rubber - Google Patents
Preparation method of butadiene-isoprene copolymer, butadiene-isoprene copolymer and tread rubber Download PDFInfo
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- CN114716598A CN114716598A CN202110002352.0A CN202110002352A CN114716598A CN 114716598 A CN114716598 A CN 114716598A CN 202110002352 A CN202110002352 A CN 202110002352A CN 114716598 A CN114716598 A CN 114716598A
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- butadiene
- isoprene
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 85
- 239000005060 rubber Substances 0.000 title claims abstract description 82
- 229920001577 copolymer Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 16
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 103
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 92
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 37
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000806 elastomer Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000463 material Substances 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
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- 238000012360 testing method Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
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- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229920003049 isoprene rubber Polymers 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
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- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
The invention discloses a preparation method of a butadiene-isoprene copolymer, the butadiene-isoprene copolymer and tread rubber. The preparation method comprises the following steps: (1) adding cyclohexane, isoprene and butadiene into a polymerization kettle, and uniformly stirring; (2) adding n-butyl lithium and a structure regulator, and reacting at 60-80 ℃ while stirring; (3) after the reaction is finished, terminating the reaction by using a polymerization inhibitor; and washing and drying to obtain polyisoprene and polyisoprene-butadiene copolymer. The butadiene-isoprene copolymer elastomer has a random structure, does not crystallize at low temperature, and can still keep high elasticity at low temperature. The butadiene-isoprene copolymer is used in the formula of the tread rubber of the winter tire to improve the cold resistance of the rubber.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and further relates to a preparation method of a butadiene-isoprene copolymer, the butadiene-isoprene copolymer and tread rubber.
Background
With the development of science and technology, the requirements of people on rubber materials are increasingly strict. In the field of winter tires, tread rubber materials thereof are required to have excellent cold resistance. The cold resistance of the rubber material is mainly determined by two aspects: the magnitude of the glass transition temperature and whether or not crystallization occurs at low temperatures. The low glass transition temperature (Tg) and the absence of crystallization at low temperatures indicate that the rubber material has excellent cold resistance.
Winter tires are widely used in some cold regions because they can better maintain the handling performance of vehicles on ice and snow covered roads. The excellent anti-ice performance is an important index for measuring the performance of the winter tire, and the anti-ice performance of the tire has close relation with the composition of a tread rubber material of the winter tire.
At present, the commonly used tread rubber materials mainly comprise styrene butadiene rubber, natural rubber and butadiene rubber, but the natural rubber and the butadiene rubber are easy to crystallize at low temperature due to the higher Tg of the styrene butadiene rubber, have poor anti-skid performance and are not suitable for being used as the tread rubber material of winter tires.
Therefore, the development of a new tread rubber material is a technical problem to be solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a butadiene-isoprene copolymer, the butadiene-isoprene copolymer and tread rubber.
Since the butadiene-isoprene copolymer itself has a low glass transition temperature, the low temperature resistance is determined by whether crystallization occurs at low temperature. The crystallinity of the rubber is determined by the randomness of the structure of the rubber material. The randomness is the random degree of the butadiene and isoprene copolymer on the copolymerization main chain, and the symmetry and the regularity of the butadiene-isoprene copolymer are reduced by a proper synthesis method, so that the crystallization capability of the copolymer is reduced and even completely lost, and the low-temperature cold resistance of the material is favorably improved.
The butadiene-isoprene copolymer elastomer has a random structure, does not crystallize at low temperature, and can be applied to low-temperature-resistant rubber compositions of tread rubber of winter tires. The invention mainly uses the method of anion solution polymerization, and adopts the structure regulation method to inhibit the crystallization behavior of the butadiene-isoprene copolymer from the basic material level, so as to synthesize the butadiene-isoprene copolymer with cis-1, 4, trans-1, 4, 3, 4-structure, and the copolymer can still keep high elasticity at low temperature. The butadiene-isoprene copolymer is used in the formula of the tread rubber of the winter tire to improve the cold resistance of the rubber.
One of the objects of the present invention is to provide a method for preparing a butadiene copolymer.
The method comprises the following steps:
(1) adding cyclohexane, isoprene and butadiene into a polymerization kettle, and uniformly stirring;
(2) n-butyl lithium and a structure regulator are stirred and reacted at the temperature of 60-80 ℃;
the structure regulator is tetrahydrofuran, diethyl ether, anisole, triethylamine or tetramethyl ethylene diamine;
(3) after the reaction is finished, terminating the reaction by using a polymerization inhibitor; washing and drying to obtain polyisoprene and polyisoprene-butadiene copolymer;
the polymerization inhibitor is methanol or ethanol.
In a preferred embodiment of the present invention,
in the step (1), the step (c),
the isoprene accounts for 50 to 100 weight percent of the total mass of the isoprene and the butadiene monomers, preferably 50 to less than 100 percent, and more preferably 50 to 80 weight percent;
the mass of the butadiene accounts for 0-50 wt% of the total mass of the isoprene and butadiene monomers, preferably more than 0-50%, and more preferably 20-50 wt%;
in a preferred embodiment of the present invention,
in the step (2),
the amount of butyl lithium accounts for 0.01-5 wt% of the total mass of the isoprene and butadiene monomers;
the amount of the structure regulator accounts for 4-6 wt% of the total mass of the isoprene and butadiene monomers;
in a preferred embodiment of the present invention,
in the step (2), the step (3),
the amount of butyl lithium accounts for 0.01-3 wt% of the total mass of the isoprene and butadiene monomers;
the amount of the structure regulator accounts for 4-6 wt% of the total mass of the isoprene and butadiene monomers.
In a preferred embodiment of the present invention,
in the step (2), the reaction time is 30-60 min; and/or the presence of a gas in the gas,
the structure regulator of the invention is tetrahydrofuran, diethyl ether, anisole, triethylamine or tetramethyl ethylene diamine. The structure regulator can regulate the content of butadiene and isoprene segment structures in the product, and the low-temperature resistance performance is best when the cir-1, 4-content in the butadiene and isoprene segments is between 30 and 70 percent. The specific results are shown in the nuclear magnetic spectrum of figure 1 and the low-temperature crystallization diagram of the expanding agent of figure 2. In the figure 2, as the crystallization density of the rubber is increased and the volume is reduced, the higher the ordinate is, the crystallization performance is good, the cold resistance is poor, wherein the cold resistance of the high cis isoprene sold in the market is the worst, and the cold resistance of the butadiene-isoprene rubber adjusted by the structure regulator is better.
Another object of the present invention is to provide a butadiene-isoprene copolymer.
The butadiene-isoprene copolymer contains: an isoprene structural unit and a butadiene structural unit;
the content of the isoprene structural unit is 50-100 wt% based on 100% of the total mass of the isoprene structural unit and the butadiene structural unit in the butadiene-isoprene copolymer; preferably 50% to less than 100%;
the content of butadiene structural units is 0-50 wt%; preferably more than 0 to 50%.
The number average molecular weight of the butadiene-isoprene copolymer is 10-20 ten thousand; the molecular weight distribution is 1.0-3.0.
In a preferred embodiment of the present invention,
the content of the isoprene structural unit is 50-80 wt% based on 100% of the total mass of the isoprene structural unit and the butadiene structural unit in the butadiene-isoprene copolymer;
the content of butadiene structural units is 20-50 wt%.
The invention also aims to provide a tread rubber.
The tread rubber is prepared from the following raw materials in parts by weight:
the total weight of the raw rubber and the butadiene-isoprene copolymer is 100 parts by weight; wherein, 1 to 50 parts by weight of butadiene-isoprene copolymer, preferably 10 to 30 parts by weight;
the raw rubber is one or more selected from raw natural rubber, raw styrene-butadiene rubber and raw cis-butadiene rubber;
the liquid rubber is liquid rubber containing butadiene chain segments; liquid isoprene rubber and liquid styrene butadiene rubber are preferred.
The liquid rubber is used as a compatilizer, so that the compatibility can be improved, and the processing performance and the mechanical property of the tread rubber are improved. The NR/BR system is mixed with commercially available liquid isoprene rubber, and the SBR/BR system is mixed with commercially available liquid styrene-butadiene rubber to improve the compatibility.
The reinforcing auxiliary agent is carbon black or white carbon black and a coupling agent; the coupling agent is silicon 69 and/or PEG4000 (polyethylene glycol 4000), and the dosage of the coupling agent can be determined by a skilled person according to actual conditions.
The processing aid can be the processing aid which is common in the prior art, such as: zinc oxide and stearic acid, and can further comprise an anti-aging agent and microcrystalline paraffin; the skilled person can determine this according to the actual situation.
The vulcanizing agent may be any of those conventionally used in the art, such as: sulfur; the amount is a conventional amount, and in the present invention, the amount is preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight.
The accelerator may be one commonly used in the art, such as: accelerator NS, accelerator D and accelerator CZ; the amount of the organic acid is a conventional amount, and the amount of the organic acid is preferably 1 to 8 parts by weight, more preferably 2 to 5 parts by weight.
The fourth purpose of the invention is to provide a preparation method of tread rubber.
The method comprises the following steps:
the tread rubber is prepared by mixing and vulcanizing the components according to the using amount.
The method comprises the following specific steps:
and 3, adding a processing aid into the raw rubber plasticated in the step 1, and then mixing for 5 minutes on an open mill.
And 4, finally adding an accelerant and a vulcanizing agent, mixing for 8min on an open mill, and thinly passing for 3-5 times.
In a preferred embodiment, in step 1, when two or more types of raw rubber are used, after the raw rubber is plasticated, the plasticated raw rubber is mixed, and then the mixture is subjected to a roll-open process, preferably 3 to 5 times by passing through a roll on a roll mill.
In a preferred embodiment, in step 3, the open mill treatment is carried out for 0.5 to 6 minutes, preferably 1 to 5 minutes, more preferably 1 to 2 minutes.
In the invention, butadiene and isoprene are taken as main monomers, and the structure is controlled by an anionic solution polymerization method to ensure that the synthesized polymer is a random copolymer, so that the crystallization behavior of the polymer at low temperature can be inhibited, the cold resistance of the polymer can be improved, and the polymer can be applied to a tread rubber material of a winter tire. The blending of a certain butadiene segment can lower the glass transition temperature of the polymer, thereby further improving the cold resistance thereof.
Compared with the prior art, the invention has the following beneficial effects:
(1) the low-temperature resistant random butadiene-isoprene copolymer improves the processability and the vulcanized rubber performance of rubber;
(2) the structure of the low-temperature resistant random butadiene-isoprene copolymer is regulated and controlled through anionic polymerization, so that the copolymer is changed into a random copolymer, the crystallization behavior at low temperature is inhibited, and the cold resistance is improved.
(3) The low-temperature resistant random butadiene-isoprene copolymer can be used as a low-temperature resistant rubber composition of a tread rubber of a winter tire;
(4) the low-temperature-resistant random butadiene-isoprene copolymer can be used as a compatilizer, and the mechanical property of a rubber product is improved.
Drawings
FIG. 1 shows a nuclear magnetic hydrogen spectrum of example 1.
It can be seen from FIG. 1 that the peak at 4.78ppm is derived from the methylene proton of 3, 4-structured isoprene. The peaks at 5.12ppm are from protons of methylene groups of isoprene of cis 1, 4-and trans 1.4-structures, and the peaks at 2.04, 1.67, 1.56ppm are from protons of methyl groups of cis 1,4-, trans 1,4-, 3, 4-structures.
Fig. 2 shows nuclear magnetic hydrogen spectra of example 2 and example 3.
It can be seen from FIG. 2 that the peak at 4.78ppm is from the methylene protons of 3, 4-structured isoprene, the peaks at 5.12, 5.36ppm are from the protons of cis 1, 4-and trans 1, 4-structured isoprene and the methylene groups of butadiene, and the peaks at 2.04, 1.67, 1.56ppm are from the protons of isoprene and the methyl groups of butadiene.
The structure of the composition can be substantially determined from the nuclear magnetic hydrogen spectrum.
FIG. 3 shows the low temperature crystallization patterns of examples 1,2,3 and commercially available high cis isoprene rubber by the swelling agent method at-25 ℃.
FIG. 4 shows stress-strain curves of the tread rubbers obtained in examples 8 to 11 and comparative example 1.
FIG. 5 shows stress-strain curves of the tread rubbers obtained in examples 12 to 16 and comparative example 2.
FIG. 6 shows stress-strain curves of the tread rubbers obtained in examples 17 to 20 and comparative example 3.
FIG. 7 shows stress-strain curves of the tread rubbers obtained in examples 21 to 25 and comparative example 4.
FIG. 8 shows compression cold resistance coefficient-time curves of the tread rubbers obtained in examples 8 to 11 and comparative example 1.
FIG. 9 shows compression cold resistance coefficient-time curves of the tread rubbers obtained in examples 12 to 16 and comparative example 2.
FIG. 10 shows compression cold resistance coefficient-time curves of the tread rubbers obtained in examples 17 to 20 and comparative example 3.
FIG. 11 shows compression cold resistance coefficient-time curves of the tread rubbers obtained in examples 21 to 25 and comparative example 4.
Wherein the higher the compression cold resistance coefficient, the better the cold resistance of the rubber.
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.
The starting materials used in the examples are all commercially available.
Example 1: preparation of low temperature resistant butadiene-pentane copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers at a molar ratio of 10:0, adding the mixed solution of the isoprene and the butadiene monomers into a treated 5L of polymerization kettle, and uniformly stirring.
And finally adding n-butyllithium and THF (structure regulator), wherein the using amount of the n-butyllithium accounts for 1.8 wt% of the total mass of the monomers, and the tetrahydrofuran accounts for 5 wt% of the total mass of the monomers. The reaction was stirred at 60 ℃ for 40 min. After the reaction is finished, ethanol is used for stopping, the polymer is condensed out, cyclohexane solution and the like are washed away, and the mixture is dried in a vacuum drying oven at the temperature of 50 ℃. Finally obtaining the Polyisoprene (PI) raw rubber. The product has calculated Mn of 21.7 ten thousand and Mw/Mn of 1.14.
Example 2: preparation of low temperature resistant butadiene-pentane copolymer
Adding 2L of cyclohexane into an absorption bottle, then adding isoprene and butadiene monomers with the molar ratio of 8:2, adding the mixed solution of the isoprene and the butadiene monomers into a treated 5L of polymerization kettle, and uniformly stirring.
And finally adding n-butyllithium and THF, wherein the using amount of the n-butyllithium accounts for 1.8 wt% of the total mass of the monomers, and the tetrahydrofuran accounts for 5 wt% of the total mass of the monomers. The reaction was stirred at 60 ℃ for 30 minutes. After the reaction is finished, ethanol is used for stopping, the polymer is condensed out, cyclohexane solution and the like are washed away, and the mixture is dried in a vacuum drying oven at the temperature of 50 ℃. Finally, the butadiene-isoprene copolymer (isoprene: butadiene-8: 2) crude rubber is obtained. The product has calculated Mn of 20.6 ten thousand and Mw/Mn of 1.17.
Example 3: preparation of low temperature resistant butadiene-pentane copolymer
Adding 2L of cyclohexane into an absorption bottle, then adding isoprene and butadiene monomers at a molar ratio of 5:5, adding the mixed solution of the isoprene and the butadiene monomers into a treated 5L of polymerization kettle, and uniformly stirring. The dosage of the n-butyl lithium accounts for 1.8 wt% of the total mass of the monomers, and the tetrahydrofuran accounts for 5 wt% of the total mass of the monomers.
The reaction was stirred at the set temperature (60 ℃) for 40 min. After the reaction is finished, terminating by using ethanol, condensing out a polymer, washing away cyclohexane solution and the like, and drying in a vacuum drying oven at 50 ℃. Finally, the crude butadiene-isoprene copolymer (SPIBP 5:5) is obtained. The product has calculated Mn 19.2 ten thousand and Mw/Mn 1.14.
Example 4: preparation of low temperature resistant butadiene-pentane copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers at a molar ratio of 5:5, adding the mixed solution into a treated 5L of polymerization kettle, and uniformly stirring.
And finally adding n-butyllithium and THF, wherein the using amount of the n-butyllithium accounts for 0.5 wt% of the total mass of the monomers, and the tetrahydrofuran accounts for 4 wt% of the total mass of the monomers. The reaction was stirred at 80 ℃ for 30 minutes. After the reaction is finished, ethanol is used for stopping, the polymer is condensed out, cyclohexane solution and the like are washed away, and the mixture is dried in a vacuum drying oven at the temperature of 50 ℃. Finally, the butadiene-isoprene copolymer (isoprene: butadiene-5: 5) crude rubber is obtained. The product has calculated Mn of 14.3 ten thousand and Mw/Mn of 1.56.
Example 5: preparation of low temperature resistant butadiene-pentane copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers at a molar ratio of 5:5, adding the mixed solution into a treated 5L of polymerization kettle, and uniformly stirring.
And finally adding n-butyllithium and THF, wherein the using amount of the n-butyllithium accounts for 3 wt% of the total mass of the monomers, and the tetrahydrofuran accounts for 6 wt% of the total mass of the monomers. The reaction was stirred at 60 ℃ for 40 minutes. After the reaction is finished, ethanol is used for stopping, the polymer is condensed out, cyclohexane solution and the like are washed away, and the mixture is dried in a vacuum drying oven at the temperature of 50 ℃. Finally, the butadiene-isoprene copolymer (isoprene: butadiene-5: 5) crude rubber is obtained. The product has calculated Mn of 30.7 ten thousand and Mw/Mn of 1.67.
Example 6: preparation of low temperature resistant butadiene-pentane copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers at a molar ratio of 5:5, adding the mixed solution into a treated 5L of polymerization kettle, and uniformly stirring.
And finally adding n-butyllithium and diethyl ether, wherein the using amount of the n-butyllithium accounts for 1.8 wt% of the total mass of the monomers, and the tetrahydrofuran accounts for 5 wt% of the total mass of the monomers. The reaction was stirred at 60 ℃ for 50 minutes. After the reaction is finished, ethanol is used for stopping, the polymer is condensed out, cyclohexane solution and the like are washed away, and the mixture is dried in a vacuum drying oven at the temperature of 50 ℃. Finally, the butadiene-isoprene copolymer (isoprene: butadiene-5: 5) crude rubber is obtained. The product has calculated Mn of 17.8 ten thousand and Mw/Mn of 1.43.
Example 7: preparation of low temperature resistant butadiene-pentane copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers at a molar ratio of 5:5, adding the mixed solution into a treated 5L of polymerization kettle, and uniformly stirring.
And finally adding n-butyllithium and anisole, wherein the using amount of the n-butyllithium accounts for 1.8 wt% of the total mass of the monomers, and the tetrahydrofuran accounts for 5 wt% of the total mass of the monomers. The reaction was stirred at 80 ℃ for 50 minutes. After the reaction is finished, ethanol is used for stopping, the polymer is condensed out, cyclohexane solution and the like are washed away, and the mixture is dried in a vacuum drying oven at the temperature of 50 ℃. Finally, the butadiene-isoprene copolymer (isoprene: butadiene-5: 5) crude rubber is obtained. The product has calculated Mn 15.4 ten thousand and Mw/Mn 1.48.
Examples 8-25 preparation of winter tire Tread rubber
(1) Plasticating raw rubber (natural rubber NR, cis-butadiene rubber BR and synthesized butadiene-isoprene copolymer), mixing the raw rubber in 3, and rolling for 4 times on an open mill;
(2) mixing carbon black, white carbon black and a coupling agent (silicon 69 and PEG4000) to obtain a filling system.
(3) Adding zinc oxide and stearic acid, mixing for 5 min, adding accelerator and vulcanizer, mixing for 8min, and thinly passing on an open mill for 3-5 times.
The specific raw material dosage is shown in tables 1-4, wherein, the two raw rubbers are BR9000, NR is commercially available rubber, and the sum of the weight of the BR9000 and the weight of the NR added with the butyl-pentyl copolymer is 100 parts. In tables 1 to 4 below, one table is one preparation batch.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
Test of mechanical Properties of Experimental examples 8 to 25
Table 5:
| shore A hardness | Elongation at break% | Tensile strength/MPa | |
| Comparative example 1 | 54 | 627 | 16 |
| Example 8 | 58 | 676 | 19 |
| Example 9 | 62 | 654 | 20 |
| Example 10 | 56 | 648 | 19 |
| Example 11 | 62 | 689 | 19 |
Table 6:
| shore A hardness | Elongation at break% | Tensile strength/MPa | |
| Comparative example 2 | 65 | 627 | 16 |
| Example 12 | 65 | 652 | 18 |
| Example 13 | 66 | 689 | 18 |
| Example 14 | 69 | 677 | 18 |
| Example 15 | 70 | 861 | 19 |
| Example 16 | 72 | 844 | 17 |
Table 7:
| shore A hardness | Elongation at break% | Tensile strength/MPa | |
| Comparative example 3 | 65 | 345 | 14 |
| Example 17 | 64 | 349 | 15 |
| Example 18 | 66 | 402 | 17 |
| Example 19 | 64 | 371 | 16 |
| Example 20 | 63 | 463 | 18 |
Table 8:
| shore A hardness | Elongation at break% | Tensile strength/MPa | |
| Comparative example 4 | 65 | 354 | 15 |
| Example 21 | 65 | 373 | 16 |
| Example 22 | 66 | 382 | 16 |
| Example 23 | 69 | 378 | 17 |
| Example 24 | 70 | 468 | 18 |
| Example 25 | 72 | 485 | 19 |
1. The tread rubbers obtained in examples 8 to 11 and comparative example 1 in Table 1 were subjected to mechanical property tests, and the results are shown in Table 5 and FIG. 4.
2. The mechanical properties of the tread rubbers obtained in examples 12 to 16 and comparative example 2 in Table 2 were measured, and the results are shown in Table 6 and FIG. 5.
3. The tread rubbers obtained in examples 17 to 20 and comparative example 3 in Table 3 were subjected to mechanical property tests, and the results are shown in Table 7 and FIG. 6.
4. The tread rubbers obtained in examples 21 to 25 and comparative example 4 in Table 4 were subjected to mechanical property tests, and the results are shown in Table 8 and FIG. 7
To compare the data: compared with comparative examples 1-4 (without the butadiene-isoprene copolymer), the mechanical property parameters of examples 4-21 of the invention are all higher than those of the comparative examples, and the mechanical property of the rubber material can be improved by mixing the butadiene-isoprene copolymer.
Test of Cold resistance in Experimental examples 8 to 25
1. The tread rubber obtained in examples 8 to 11 and comparative example 1 in table 1 was subjected to a cold resistance test, and the results are shown in fig. 8.
2. The cold resistance tests of the tread rubbers obtained in examples 12 to 16 and comparative example 2 in Table 2 were carried out, and the results are shown in FIG. 9.
3. The tread rubbers obtained in examples 17 to 20 and comparative example 3 in Table 3 were subjected to a cold resistance test, and the results are shown in FIG. 10.
4. Cold resistance tests were performed on the tread rubbers obtained in examples 21 to 25 and comparative example 4 in Table 4, and the results are shown in FIG. 11
As can be seen from FIGS. 8 to 11, when the tread rubber is mixed into the butadiene-isoprene copolymer, the cold resistance coefficient increases, which means that the cold resistance is improved. In conclusion, the low-temperature-resistant butadiene-isoprene copolymer elastomer synthesized by adopting the anionic polymerization process has lower glass transition temperature and no crystallization at low temperature, has excellent low-temperature resistance compared with the commercially available common tread rubber compound, and has greater development potential in the field of winter tire tread rubber.
Claims (10)
1. A method of producing a butadiene copolymer, characterized in that the method comprises:
(1) adding cyclohexane, isoprene and butadiene into a polymerization kettle, and uniformly stirring;
(2) adding n-butyl lithium and a structure regulator, and reacting at the temperature of 60-80 ℃ while stirring;
the structure regulator is tetrahydrofuran, diethyl ether, anisole, triethylamine or tetramethyl ethylene diamine;
(3) after the reaction is finished, terminating the reaction by using a polymerization inhibitor; washing and drying to obtain polyisoprene and polyisoprene-butadiene copolymer;
the polymerization inhibitor is methanol or ethanol.
2. The method of claim 1, wherein:
in the step (1), the step (c),
the isoprene accounts for 50-100 wt%, preferably 50-80 wt% of the total mass of the isoprene and butadiene monomers;
the mass of butadiene is 0-50 wt%, preferably 20-50 wt%, of the total mass of isoprene and butadiene monomers.
3. The method of claim 1, wherein:
in the step (2),
the consumption of butyl lithium accounts for 0.01 to 5 weight percent of the total mass of the isoprene and butadiene monomers;
the amount of the structure regulator accounts for 4-6 wt% of the total mass of the isoprene and butadiene monomers.
4. The method of claim 4, wherein:
in the step (2),
the amount of butyl lithium accounts for 0.01-3 wt% of the total mass of the isoprene and butadiene monomers;
the amount of the structure regulator accounts for 4-6 wt% of the total mass of the isoprene and butadiene monomers.
5. The method of claim 1, wherein:
in the step (2), the reaction time is 30-60 min.
6. A butadiene-isoprene copolymer obtained by the production method according to any one of claims 1 to 5, wherein:
the butadiene-isoprene copolymer contains: an isoprene structural unit and a butadiene structural unit;
based on 100 percent of the total mass of the isoprene structural units and the butadiene structural units in the butadiene-isoprene copolymer,
the content of isoprene structural units is 50-100 wt%;
the content of butadiene structural units is 0-50 wt%;
the number average molecular weight of the butadiene-isoprene copolymer is 10-20 ten thousand; the molecular weight distribution is 1.0-3.0.
7. A butadiene-pentane copolymer according to claim 6, wherein:
based on 100 percent of the total mass of the isoprene structural units and the butadiene structural units in the butadiene-isoprene copolymer,
the content of isoprene structural units is 50-80 wt%;
the content of butadiene structural units is 20-50 wt%.
8. A tread rubber containing the butadiene-isoprene copolymer of any one of claims 6 to 7, wherein the tread rubber is prepared from the following raw materials in parts by weight:
the total weight of the raw rubber and the butadiene-isoprene copolymer is 100 parts by weight; wherein, 1 to 50 parts by weight of the butyl-pentyl copolymer, preferably 10 to 30 parts by weight;
9. a tread band as defined by claim 8 wherein:
the raw rubber is one or more selected from raw natural rubber, raw styrene-butadiene rubber and raw cis-butadiene rubber; and/or
The liquid rubber is liquid rubber containing butadiene chain segments; and/or the presence of a gas in the gas,
the reinforcing auxiliary agent is carbon black or white carbon black and a coupling agent.
10. A method for preparing a tread rubber for a winter tyre according to any one of claims 8 to 9, characterized in that: the method comprises the following steps:
the tread rubber is prepared by mixing and vulcanizing the components according to the using amount.
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